Emulsifier components and methods of using the same

ABSTRACT

This invention relates to an additive comprising a functional group derived from a first hydrocarbyl-substituted acylating agent and a functional group derived from a second hydrocarbyl-substituted acylating agent, where the functional groups are coupled by a functional group derived from an alkylene glycol. The invention also relates to an emulsifier component prepared by a process that utilizes the described additive and converts it to an emulsifier component by reacting it with a neutralizing component. The invention also relates to a process of making the described emulsifier component, and a method of customizing an emulsifier component in a composition by using the described additive and the described process for converting it to the described emulsifier component.

This invention relates to an additive comprising a functional groupderived from a first hydrocarbyl-substituted acylating agent and afunctional group derived from a second hydrocarbyl-substituted acylatingagent, where the functional groups are coupled by a functional groupderived from an alkylene glycol, and in certain embodiments a linearalkylene glycol. The invention also relates to an emulsifier componentprepared by a process that utilizes the described additive and convertsit to an emulsifier component by reacting it with a neutralizingcomponent. The invention also relates to a process of making thedescribed emulsifier component, and a method of customizing anemulsifier component in a composition by using the described additiveand the described process for converting it to the described emulsifiercomponent.

BACKGROUND OF THE INVENTION

Hydrocarbyl-substituted carboxylic acylating agents having at leastabout 30 aliphatic carbon atoms in the substituent are known asadditives in normally liquid fuels and lubricants. Examples of suchacylating agents include the polyisobutenyl-substituted succinic acidsand anhydrides. The use of such carboxylic acylating agents as additivesin normally liquid fuels and lubricants is disclosed in U.S. Pat. Nos.3,288,714 and 3,346,354.

These acylating agents are also useful as intermediates for preparingadditives for use in normally liquid fuels and lubricants as describedin U.S. Pat. Nos. 2,892,786; 3,087,936; 3,163,603; 3,172,892; 3,189,544;3,215,707; 3,219,666; 3,231,587; 3,235,503; 3,272,746; 3,306,907;3,306,908; 3,331,776; 3,341,542; 3,346,354; 3,374,174; 3,379,515;3,381,022; 3,413,104; 3,450,715; 3,454,607; 3,455,728; 3,476,686;3,513,095; 3,523,768; 3,630,904; 3,632,511; 3,697,428; 3,755,169;3,804,763; 3,836,470; 3,862,981; 3,936,480; 3,948,909; 3,950,341;4,234,435; and 4,471,091; and French Patent 2,223,415.

U.S. Pat. No. 3,216,936 describes nitrogen-containing dispersants foruse in lubricants which are obtained by the reaction of an alkyleneamine with an acidic mixture consisting of a hydrocarbon-substitutedsuccinic acid having at least about 50 aliphatic carbon atoms in thehydrocarbon substituent and an aliphatic monocarboxylic acid. Thealiphatic monocarboxylic acids are described as including saturated andunsaturated acids such as acetic acid, dodecanoic acid, oleic acid,naphthenic acid, formic acid, etc. Acids having 12 or more aliphaticcarbon atoms, particularly stearic acid and oleic acid, are described asbeing especially useful.

U.S. Pat. Nos. 3,639,242 and 3,708,522 describe compositions prepared bypost-treating mono- and polycarboxylic acid esters with mono- orpolycarboxylic acid acylating agents. The compositions thus obtained arereported to be useful as dispersants in lubricants and fuels.

U.S. Pat. No. 4,642,330 discloses dispersant salt compositions made byreacting phosphorus-free carboxylic solubilizers with sulfonic acid-freeorganic acids or mineral acids. The carboxylic solubilizer is thereaction product of a polycarboxylic acid acylating agent having atleast one hydrocarbon-based substituent of at least 8 to 500 carbonatoms with at least one poly(alkyleneamine). The reference indicatesthat these dispersant salt compositions have good thermal stability whenmixed with a surfactant or a hydrophilic organic solvent, and that theycan be used with aqueous solutions to disperse various fillers includingcarbon black and to solubilize various fluids.

Nitrogen-containing, phosphorus-free carboxylic solubilizers useful inwater based functional fluids are disclosed in U.S. Pat. Nos. 4,329,249;4,368,133; 4,435,297; 4,447,348; and 4,448,703. These solubilizers aremade by reacting (I) at least one carboxylic acid acylating agent havingat least one hydrocarbyl substituent of from about 12 to about 500carbon atoms with (II) at least one (a) N-(hydroxyl-substitutedhydrocarbyl) amine, (b) hydroxyl-substituted poly(hydrocarbyloxy) analogof said amine (a), or (c) mixtures of (a) and (b). These patentsindicate that preferred acylating agents include the substitutedsuccinic acids or anhydrides, such as polyisobutenyl-substitutedsuccinic anhydride, and that the amines that are useful include theprimary, secondary and tertiary alkanol amines, such asdiethylethanolamine and mixtures of diethylethanolamine andethanolamine. These solubilizers are useful in dispersing oil-soluble,water-insoluble functional additives in water-based functional fluids.

U.S. Pat. No. 5,047,175 discloses salt compositions comprising: (A) atleast one salt moiety derived from (A)(I) at least one high-molecularweight polycarboxylic acylating agent, said acylating agent (A)(I)having at least one hydrocarbyl substituent having an average of fromabout 20 to about 500 carbon atoms, and (A)(II) ammonia, at least oneamine, at least one alkali or alkaline earth metal, and/or at least onealkali or alkaline earth metal compound; (B) at least one salt moietyderived from (B)(I) at least one low-molecular weight polycarboxylicacylating agent, said acylating agent (B)(I) optionally having at leastone hydrocarbyl substituent having an average of up to about 18 carbonatoms, and (B)(II) ammonia, at least one amine, at least one alkali oralkaline earth metal, and/or at least one alkali or alkaline earth metalcompound; said components (A) and (B) being coupled together by (C) atleast one compound having (i) two or more primary amino groups, (ii) twoor more secondary amino groups, (iii) at least one primary amino groupand at least one secondary amino group, (iv) at least two hydroxylgroups or (v) at least one primary or secondary amino group and at leastone hydroxyl group. These salt compositions are useful as emulsifiers inwater-in-oil explosive emulsions, particularly cap-sensitive explosiveemulsions.

U.S. Pat. No. 4,828,633 discloses emulsion explosives based upon theemulsifier of U.S. Pat. No. 5,047,175.

U.S. Pat. No. 5,422,024 provides for aqueous oil-in-water emulsionfunctional fluids comprising water, an oil and an emulsifying quantityof a salt composition comprising: (A) at least one salt moiety derivedfrom (A)(I) at least one high-molecular weight polycarboxylic acylatingagent, said acylating agent (A)(I) having at least one hydrocarbylsubstituent having an average of from about 20 to about 200 carbonatoms, and (A)(II) ammonia, at least one amine, at least one alkali oralkaline earth metal, and/or at least one alkali or alkaline earth metalcompound; (B) at least one salt moiety derived from (B)(I) at least onelow-molecular weight polycarboxylic acylating agent, said acylatingagent (B)(I) optionally having at least one hydrocarbyl substituenthaving an average of average of up to about 18 carbon atoms, and (B)(II)ammonia, at least one amine, at least one alkali or alkaline earthmetal, and/or at least one alkali or alkaline earth metal compound; saidcomponents (A) and (B) being coupled together by (C) least one compoundhaving (i) two or more primary amino groups, (ii) two or more secondaryamino groups, (iii) at least one primary amino group and at least onesecondary amino group, (iv) at least two hydroxyl groups or (v) at leastone primary or secondary amino group at least one hydroxyl group.

These materials described above have proven to be useful emulsifiershowever there is continued need for emulsifiers with improvedperformance, as well as emulsifier systems that are more easilycustomized for specific applications. There is a need to allow the fluidusers and/or manufacturers the ability to easily adjust and/or adapt theemulsifier they are using based on the specific fluid and/or end usethey are dealing with. Thus there is a continued need for betterperforming and/or more customizable emulsifiers which can be customizedby the fluid users and/or manufacturers.

SUMMARY OF THE INVENTION

The disclosed technology provides an additive comprising (i) afunctional group derived from a first hydrocarbyl-substituted acylatingagent and (ii) a functional group derived from a secondhydrocarbyl-substituted acylating agent, where the functional groups (i)and (ii) are coupled by a functional group derived from an alkyleneglycol such as a linear alkylene glycol; wherein the firsthydrocarbyl-substituted acylating agent comprises a hydrocarbylsubstituent group containing at least 20 carbon atoms; and wherein thesecond hydrocarbyl-substituted acylating agent comprises a hydrocarbylsubstituent group containing less than 20 carbon atoms.

The invention further provides the described additive where the firsthydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight greater than 400. In some embodiments, long chain hydrocarbon hasa number average molecular weight greater than 450, at least 500, atleast 750, or even at least 800. (A “monounsaturated carboxylic acid”refers to a carboxylic acid that contains one ethylenic unsaturation,that is, not counting the carbonyl double bond.)

The invention further provides the described additive where the firsthydrocarbyl-substituted acylating agent comprises polyisobutylenesuccinic anhydride having a number average molecular weight greater than400. In some embodiments, the polyisobutylene succinic anhydride has apolyisobutylene group with a number average molecular weight greaterthan 450, at least 500, at least 750, or even at least 800.

The invention further provides the described additive wherein the secondhydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight less than 400 or less than 280 or less than 250. In someembodiments, long chain hydrocarbon has a number average molecularweight from 100 to 400, or from 200 to 400, or from 200 to 280, or from200 to 250, or from 300 to 400, or even from 300 to 350, or even about322.

The invention further provides the described additive wherein the secondhydrocarbyl-substituted acylating agent comprises hexadecenyl succinicanhydride.

The invention further provides the described additive wherein thealkylene glycol comprises a glycol having of the general formulaHO(C(R))_(x)—O_(m)—H wherein each R is independently H or an alkylgroup of 1 to 6 carbon atoms each x is independently an integer from 2to 10 and m is an integer from 1 to 10. That is, some or all of the Rgroups may be H and the remainder (if any) of the R groups may be saidalkyl groups. In certain embodiments disclosed herein, one or more ofthe R groups may be methyl groups. In certain embodiments throughoutthis document, the number of carbon atoms in the glycol of the foregoingstructure will be less than 400, or less than 200, or less than 100, or2 to 50, or 2 to 10, or 2 or 3.

In some embodiments, the alkylene glycol is a linear alkylene glycol,and in some embodiments it comprises ethylene glycol.

The invention further provides the described additive wherein the firsthydrocarbyl-substituted acylating agent comprises polyisobutylenesuccinic anhydride having a number average molecular weight greater than750; wherein the second hydrocarbyl-substituted acylating agentcomprises hexadecenyl succinic anhydride; and wherein the alkyleneglycol comprises ethylene glycol.

The invention further provides an emulsifier component prepared by aprocess comprising the steps of: Step (I) reacting a firsthydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an (optionally linear)alkylene glycol; wherein the first hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing at least 20carbon atoms; and wherein the second hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing less than 20carbon atoms; resulting in an additive comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; Step (II)providing said additive for use as an emulsifier component precursor;and Step (III) converting said additive to an emulsifier component byreacting said additive with a neutralizing component. Any of theadditives described herein may be prepared and used as described by thisprocess.

The invention further provides the emulsifier component described abovewhere said neutralizing component comprises an alkali or alkalineearth-metal base or an amine. Suitable amines include NaOH, KOH,monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, butylethanolamine, butyldiethanolamine, octyl diethanolamine, cyclohexyl diethanolamine,monoisopropanolamine, diispropanolamine, triispropanolamine,diglycolamine, 1-amino-2-methyl-1-propanol, 3-amino-4-octanol,dicylcohexylamine, octylamine, and any combinations thereof.

The invention further provides a process of making an emulsifiercomponent comprising the steps of: Step (I) reacting a firsthydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an (optionally linear)alkylene glycol; wherein the first hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing at least 20carbon atoms; and wherein the second hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing less than 20carbon atoms; resulting in an intermediate (which may also be referredto throughout this document as an additive) comprising (i) a functionalgroup derived from said first hydrocarbyl-substituted acylating agentand (ii) a functional group derived from said secondhydrocarbyl-substituted acylating agent, where the functional groups (i)and (ii) are coupled by a functional group derived from said alkyleneglycol; Step (II) providing said additive for use as an emulsifiercomponent precursor; and, typically thereafter, Step (III) convertingsaid intermediate (or additive) to an emulsifier component by reactingsaid intermediate (additive) with a neutralizing component. Any of theadditives described herein may be prepared and used as described by thisprocess.

The invention further provides the describe process wherein the firsthydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight greater than 400; and wherein the second hydrocarbyl-substitutedacylating agent comprises the reaction product of a long chainhydrocarbon with a monounsaturated carboxylic acid; wherein said longchain hydrocarbon has a number average molecular weight less than 400 orless than 280; wherein the (optionally linear) alkylene glycol comprisesa glycol having of the general formula HO(C(R))_(x)—O_(m)—H whereineach R is independently H or an alkyl group of 1 to 6 carbon atoms, eachx is independently an integer from 2 to 10 and m is an integer from 1 to10.

The invention further provides the describe process wherein the firsthydrocarbyl-substituted acylating agent comprises polyisobutylenesuccinic anhydride having a number average molecular weight greater than750; wherein the second hydrocarbyl-substituted acylating agentcomprises hexadecenyl succinic anhydride; and wherein the alkyleneglycol comprises ethylene glycol.

The invention further provides a method of customizing an emulsifiercomponent in a composition said method comprising the steps of: Step (I)preparing an additive by reacting a first hydrocarbyl-substitutedacylating agent, a second hydrocarbyl-substituted acylating agent, andan (optionally linear) alkylene glycol; wherein the firsthydrocarbyl-substituted acylating agent comprises a hydrocarbylsubstituent group containing at least 20 carbon atoms; and wherein thesecond hydrocarbyl-substituted acylating agent comprises a hydrocarbylsubstituent group containing less than 20 carbon atoms; resulting in anadditive comprising (i) a functional group derived from said firsthydrocarbyl-substituted acylating agent and (ii) a functional groupderived from said second hydrocarbyl-substituted acylating agent, wherethe functional groups (i) and (ii) are coupled by a functional groupderived from said alkylene glycol; Step (II) supplying said additiveinto a composition that requires an emulsifier component; and, typicallythereafter, Step (III) converting said additive, in said composition, toan emulsifier component by reacting said additive with a neutralizingcomponent; resulting in a customized emulsifier component. Any of theadditives described herein may be prepared and used as described by thismethod.

The invention further provides the described method wherein the firsthydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight greater than 400; and wherein the second hydrocarbyl-substitutedacylating agent comprises the reaction product of a long chainhydrocarbon with a monounsaturated carboxylic acid; wherein said longchain hydrocarbon has a number average molecular weight less than 400 orless than 280; and wherein the alkylene glycol comprises a glycol havingof the general formula HO(CH₂)_(x)—O_(m)—H wherein each R isindependently H or an alkyl group of 1 to 6 carbon atoms each x isindependently an integer from 2 to 10 and m is an integer from 1 to 10.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration.

It has been found that using the described additive provides a benefitto emulsifier users, by allowing the user to optimize theHydrophilic-Lipophilic Balance (HLB), buffering system and corrosioninhibition system of the additive resulting in an emulsifier customizedfor use in the specific metalworking product and/or application relevantto the user. This approach involves the use of an additive that hasnever been used as an emulsifier itself, which may then be furthermodified by emulsifier users to achieve the specific emulsifierperformance they desire.

The Additive

The disclosed technology provides an additive comprising (i) afunctional group derived from a first hydrocarbyl-substituted acylatingagent and (ii) a functional group derived from a secondhydrocarbyl-substituted acylating agent, where the functional groups (i)and (ii) are coupled by a functional group derived from an alkyleneglycol which may be either a branched or a linear alkylene glycol;wherein the first hydrocarbyl-substituted acylating agent comprises ahydrocarbyl substituent group containing at least 20 carbon atoms; andwherein the second hydrocarbyl-substituted acylating agent comprises ahydrocarbyl substituent group containing less than 20 carbon atoms.

The first hydrocarbyl-substituted acylating agent and the secondhydrocarbyl-substituted acylating agent, from which the functionalgroups (i) and (ii) are derived, may also be described as carboxylicacylating agents and may be aliphatic or aromatic, polycarboxylic acidsor acid-producing compounds. As used herein, the term “carboxylicacylating agent” is intended to include carboxylic acids as well asacid-producing derivatives thereof such as anhydrides, esters, acylhalides and mixtures thereof, unless otherwise specifically stated.

The acylating agents may contain polar substituents provided that thepolar substituents are not present in portions sufficiently large toalter significantly the hydrocarbon character of the acylating agent.Typical suitable polar substituents include halo, such as chloro andbromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio, nitro, etc. Suchpolar substituents, if present, preferably do not exceed about 10% byweight of the total weight of the hydrocarbon portion of the acylatingagent, exclusive of the carboxyl groups.

Examples of low molecular weight polycarboxylic acids, (i.e., the secondhydrocarbyl-substituted acylating agent which comprises a hydrocarbylsubstituent group containing less than 20 carbon atoms), includedicarboxylic acids and derivatives such as maleic acid, maleicanhydride, chloromaleic anhydride, malonic acid, succinic acid, succinicanhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid,azelaic acid, sebacic acid, glutaconic acid, citraconic acid, itaconicacid, allyl succinic acid, cetyl malonic acid,tetrapropylene-substituted succinic anhydride, etc. Lower alkyl estersof these acids can also be used.

In some embodiments, both the first hydrocarbyl-substituted acylatingagent and the second hydrocarbyl-substituted acylating agents arehydrocarbyl substituted succinic acids and anhydrides.

The hydrocarbyl succinic acylating agents may contain polar substituentsprovided that the polar substituents are not present in portionssufficiently large to alter significantly the hydrocarbon character ofthe acylating agent. Typical suitable polar substituents include halo,such as chloro and bromo, oxo, oxy, formyl, sulfenyl, sulfinyl, thio,nitro, etc. Such polar substituents, if present, preferably do notexceed about 10% by weight of the total weight of the hydrocarbonportion of the acylating agent, exclusive of the carboxyl groups.

The high-molecular weight polycarboxylic acylating agents (i.e. thefirst hydrocarbyl-substituted acylating agent which comprises ahydrocarbyl substituent group containing at least 20 carbon atoms), arewell known in the art and have been described in detail, for example, inU.S. Pat. Nos. 3,215,707; 3,231,587; 3,288,714; 3,346,354; 3,912,764;4,110,349; and 4,234,435; and British Patent 1,492,337. These patentsare incorporated herein by reference.

The hydrocarbyl groups of the first and second hydrocarbyl-substitutedacylating agents are not overly limited so long as they meet therequirements described herein. Especially useful hydrocarbyl groupscomprising polymers of 1-mono-olefins such as ethylene, propene,1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene,3-cyclohexyl-1-butene, and 2-methyl-5-propyl-1-hexene. Polymers ofmedial olefins, i.e., olefins in which the olefinic linkage is not atthe terminal position, likewise are useful. These are exemplified by2-butene, 3-pentene, and 4-octene. Interpolymers of 1-mono-olefins suchas illustrated above with each other and with other interpolymerizableolefinic substances such as aromatic olefins, cyclic olefins, andpolyolefins, are also useful. Such interpolymers include for example,those prepared by polymerizing isobutene with styrene, isobutene withbutadiene, propene with isoprene, propene with isobutene, ethylene withpiperylene, isobutene with chloroprene, isobutene with p-methyl-styrene,1-hexene with 1,3-hexadiene, 1-octene with 1-hexene, 1-heptene with1-pentene, 3-methyl-1-butene with 1-octene, 3,3-dimethyl- l -pentenewith 1-hexene, isobutene with styrene and piperylene, etc.

For reasons of hydrocarbon solubility, the interpolymers contemplatedfor use in preparing the acylating agents of this invention arepreferably substantially aliphatic and substantially saturated, that is,they should contain at least about 80% and preferably about 95%, on aweight basis, of units derived from aliphatic mono-olefins. Preferably,they will contain no more than about 5% olefinic linkages based on thetotal number of the carbon-to-carbon covalent linkages present.

In one embodiment of the invention, the polymers are obtained by thepolymerization of a C4 refinery stream having a butene content of about35% to about 75% by weight and an isobutene content of about 30% toabout 60% by weight. These polyisobutenes preferably containpredominantly (that is, greater than about 80% of the total repeatunits) isobutene repeat units of the configuration —CH₂C(CH₃)₂—. Thehydrocarbons and ethylenically unsaturated hydrocarbons used in thepreparation of the higher molecular weight succinic acylating agents mayhave up to about 200 carbon atoms per molecule. Some acylating agentsare those containing hydrocarbyl groups of from about 20 to about 150,or from 30 to about 120, or from about 50 to about 80 carbon atoms. Thehydrocarbyl-substituted succinic acids and the anhydride may prepared byreacting maleic anhydride with a high molecular weight olefin. Thehydrocarbyl-substituted succinic anhydrides may be hydrolyzed bytreatment with water or steam to the corresponding acid and either theanhydride or the acid may be converted to the corresponding acid orester.

The hydrocarbyl group of the first hydrocarbyl-substituted acylatingagent may contain from about 20 to about 200 carbon atoms, from about 30to about 150 carbon atoms, from about 50 to about 200 carbon atoms, oreven from about 70 to about 80 carbon atoms.

The second hydrocarbyl-substituted acylating agent, which may also bereferred to as the low molecular weight succinic acylating agents can beprepared in essentially the same manner as the high molecular weightmaterials. In some embodiments, its hydrocarbyl group is an aliphatic oralicyclic hydrocarbyl group with less than about 10% of itscarbon-to-carbon bonds being unsaturated. Its hydrocarbyl can be derivedfrom olefins of from 2 to about 18 carbon atoms with alpha-olefins beingparticularly useful. Examples of such olefins include ethylene,propylene, 1-butene, isobutene, 1-pentene, 2-methyl-1-butene,3-methyl-1-butene, 1-hexene, 1-heptene, 1-octene, styrene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene.

Commercially available alpha olefin fractions such as C12-18alpha-olefins, C12-16 alpha-olefins, C14-14 16 alpha-olefins, C14-18alpha-olefins, and C16-18 alpha-olefins, are particularly useful. Thesecommercial alpha-olefin fractions also usually include minor amounts ofalpha-olefins outside the given ranges. As is the case for the highmolecular weight materials, the unsaturated material or optionallychlorinated analog is reacted with maleic acid or maleic anhydride. Theproduction of such substituted succinic acids and their derivatives iswell known to those of skill in the art and need not be discussed indetail herein.

In some embodiments, the first hydrocarbyl-substituted acylating agentcomprises the reaction product of a long chain hydrocarbon with amonounsaturated carboxylic acid; wherein said long chain hydrocarbon hasa number average molecular weight greater than 400. In some embodiments,long chain hydrocarbon has a number average molecular weight greaterthan 450, at least 500, at least 750, or even at least 800. In someembodiments, the first hydrocarbyl-substituted acylating agent comprisespolyisobutylene succinic anhydride having a number average molecularweight greater than 400. In some embodiments, the polyisobutylenesuccinic anhydride has a number average molecular weight greater than450, at least 500, at least 750, or even at least 800.

In some embodiments, the second hydrocarbyl-substituted acylating agentcomprises the reaction product of a long chain hydrocarbon with amonounsaturated carboxylic acid; wherein said long chain hydrocarbon hasa number average molecular weight less than 400 or less than 280. Insome embodiments, long chain hydrocarbon has a number average molecularweight from 100 to 400, or from 200 to 400, or from 300 to 400, or evenfrom 300 to 350, or even about 322, or 100 to less than 280. In someembodiments, the second hydrocarbyl-substituted acylating agentcomprises hexadecenyl succinic anhydride.

The functional groups (i) and (ii) described above are coupled by afunctional group derived from an alkylene glycol. This third functionalgroup acts as a bridge between the low and the high molecular weightfunctional groups derived from the acylating agents described above. Thelow and high molecular weight agents may be mixed together, and arereacted with the bridging molecule. The reaction is such that thepredominant species in the reaction mixture is the product in which thealkylene glycol acts as a bridge between a first hydrocarbyl-substitutedacylating agent and a second hydrocarbyl-substituted acylating agent.However, there may be some formation of molecules in which two lowmolecular weight succinic agents are linked as well as formation ofspecies in which two high molecular weight succinic agents are linked.In some embodiments low and high molecular weight agents may be reactedsequentially with the alkylene glycol. In this case, the speciescomprising a first hydrocarbyl-substituted acylating agent and a secondhydrocarbyl-substituted acylating agent molecule linked by an alkyleneglycol greatly predominates over the other species.

In general, any compound having (i) two or more primary amino groups,(ii) two or more secondary amino groups, (iii) at least one primaryamino group and at least one secondary amino group, (iv) at least twohydroxyl groups, or (v) at least one primary or secondary amino groupand at least one hydroxyl group may be used as a linking group. However,in the present invention, it has been found that using an alkyleneglycol, such as, in some embodiments, a linear alkylene glycol, providesthe best results, i.e. the most customizable additive.

The alkylene glycols useful in the invention may also be referred togenerally as polyols, and includes those compounds of the generalformula: R¹(OH)_(m) wherein R¹ is a divalent organic group joined to the—H groups through carbon-to-oxygen bonds (that is, —COH wherein thecarbon is not part of a carbonyl group) and m is 2. These alcohols arebe aliphatic and in some embodiments contain not more than about 40, ornot more than about 20 carbon atoms.

Alcohols useful in this invention include alkylene glycols with thealkylene group containing from about 2 to 10 or 2 to 8 carbon atoms.They may also include polyoxyalkylene glycol, that is, materialsrepresented by HO(C(R))_(x)—O_(m)—H where each R is independently H oran alkyl group of 1 to 6 carbon atoms each x is independently an integerfrom 2 to about 10 and m is an integer greater than 1, that is, 2 to 10.They are illustrated, for example, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, dibutylene glycol, tributylene glycol, and otheralkylene glycols and polyoxyalkylene glycols in which the alkylenegroups contain from 2 to about 8 carbon atoms. Polyoxyalkylene glycolswhich are copolymers of different alkylene oxide units may also be used,such as copolymers of ethylene glycol and propylene glycols such as 1,2-or 1,3-propylene glycol. They may be referred to as alkylene glycols asan alternative to the nomenclature “polyalkylene glycol”—both suchmaterials may be used. Such materials may also be referred to asoligomers, since the number of repeat units will typically not exceed10. In one embodiment the linear alkylene glycol comprises apoly(ethylene glycol), a poly(1,3-propylene glycol) or a copolymer ofethylene glycol and 1,3-propylene glycol.

In some embodiments, one or more linking compounds is used incombination with linear alkylene glycols described herein. Suchadditional linker may include any compound having (i) two or moreprimary amino groups, (ii) two or more secondary amino groups, (iii) atleast one primary amino group and at least one secondary amino group,(iv) at least two hydroxyl groups, or (v) at least one primary orsecondary amino group and at least one hydroxyl group may be used as alinking group. In other embodiments, the linking compounds contains thealkylene glycols described herein, and is essentially free of, or evencompletely free of, any other linking compounds.

In some embodiments, the described additive wherein the alkylene glycolcomprises a glycol having of the general formula HO(CH₂)_(x)OH wherein xis an integer from 2 to 10. In some embodiments, the alkylene glycolcomprises ethylene glycol.

The invention further provides the described additive wherein the firsthydrocarbyl-substituted acylating agent comprises polyisobutylenesuccinic anhydride having a number average molecular weight greater than750; wherein the second hydrocarbyl-substituted acylating agentcomprises hexadecenyl succinic anhydride; and wherein the alkyleneglycol comprises ethylene glycol.

In some embodiments, the first hydrocarbyl-substituted acylating agentcomprises the reaction product of a long chain hydrocarbon with amonounsaturated carboxylic acid; wherein said long chain hydrocarbon hasa number average molecular weight greater than 400; and the secondhydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight less than 400 or less than 280; and the alkylene glycol comprisesa glycol having of the general formula HO(C(R))_(x)—O_(m)—H where eachR is independently H or an alkyl group of 1 to 6 carbon atoms each x isindependently an integer from 2 to about 10 and m is an integer from 1to about 10.

In some embodiments, the first hydrocarbyl-substituted acylating agentcomprises polyisobutylene succinic anhydride having a number averagemolecular weight greater than 750; the second hydrocarbyl-substitutedacylating agent comprises hexadecenyl succinic anhydride; and thealkylene glycol comprises ethylene glycol.

The Emulsifier Component

The invention further provides an emulsifier component prepared by aprocess that allows for the customization of the emulsifier. Theemulsifier component is prepared by: Step (I) reacting a firsthydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an (optionally linear)alkylene glycol; wherein the first hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing at least 20carbon atoms; and wherein the second hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing less than 20carbon atoms; resulting in an additive comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; then Step (II)providing said additive for use as an emulsifier component precursor;and (typically thereafter) Step (III) converting said additive to anemulsifier component by reacting said additive with a neutralizingcomponent. The emulsifier component described herein may be preparedusing any of the additives described herein, where the additive is theemulsifier component precursor that is then converted into theemulsifier component.

In Step (II), by providing said additive for use as an emulsifiercomponent precursor, it is meant that the emulsifier component precursor(which may also be referred to as the additive) is handled like aconventional emulsifier component would be. However, in the case of theemulsifier component precursor, it is converted into the specificemulsifier component of a downstream party's choice, for example, afinished fluid blender and/or user, who follows Step (III) and convertthe additive to an emulsifier component by reacting said additive with aneutralizing component.

In some embodiments, providing said additive for use as an emulsifiercomponent precursor involves using, storing, transporting, selling,blending, and/or otherwise handing the additive before it is convertedinto the emulsifier component. In some embodiments, the emulsifiercomponent precursor is transported and/or stored after the additive isformed, but before the additive is converted to the emulsifiercomponent.

The neutralizing components used to form the emulsifier componentsdescribed above are not overly limited. Typically, the resultingemulsifier component is in the form of a salt. The emulsifier componentsmay be formed from mixtures of one or more neutralizing components. Insome embodiments, a single kind of neutralizing component is used. Inother embodiments, a mixture of two or more neutralizing components areused.

The metals useful as neutralizing components include the alkali andalkaline earth-metals that may be found in metal bases. The aminesuseful as neutralizing components in preparing the salt compositions ofthe invention include ammonia, and the primary amines, secondary aminesand hydroxyamines. In addition to ammonia, the primary amines, secondaryamines and hydroxyamines, the amines useful as neutralizing componentsalso include primary and secondary monoamines, and tertiary mono- andpolyamines. Useful primary and secondary monoamines include aliphatic,cycloaliphatic and aromatic monoamines. The tertiary amines areanalogous to the primary amines, secondary amines and hydroxyamines withthe exception that they can be either monoamines or polyamines and thehydrogen atoms in the H—N< or —NH₂ groups are replaced by hydrocarbylgroups.

Useful polyamines include are characterized by the presence within theirstructure of at least two —NH₂ groups, at least two >NH groups, or atleast one —NH₂ group and at least one >NH group. These polyamines can bealiphatic, cycloaliphatic, aromatic or heterocyclic, includingaliphatic-substituted aromatic, aliphatic-substituted cycloaliphatic,aliphatic-substituted heterocyclic, cycloaliphatic-substitutedaliphatic, cycloaliphatic-substituted aromatic,cycloaliphatic-substituted heterocyclic, aromatic-substituted aliphatic,aromatic-substituted cycloaliphatic, aromatic-substituted heterocyclic,heterocyclic-substituted aliphatic, heterocyclic-substitutedcycloaliphatic and heterocyclic-substituted aromatic amines. Theseamines may be saturated or unsaturated. If unsaturated, the amine ispreferably free from acetylenic unsaturation. These amines may alsocontain non-hydrocarbon substituents or groups as long as these groupsdo not significantly interfere with the reaction. Such non-hydrocarbonsubstituents or groups include lower alkoxy, lower alkyl, mercapto,nitro, and interrupting groups such as —O— and —S—. The polyaminesinclude aliphatic, cycloaliphatic and aromatic polyamines analogous tothe aliphatic, cycloaliphatic and aromatic monoamines described belowexcept for the presence within their structure of at least oneadditional >NH or —NH₂ group.

Aliphatic monoamines include mono-aliphatic and di-aliphatic-substitutedamines wherein the aliphatic groups can be saturated or unsaturated andstraight or branched chain. Thus, they are primary or secondaryaliphatic amines. Such amines include, for example, mono- anddi-alkyl-substituted amines, mono- and di-alkenyl-substituted amines,and amines having one N-alkenyl substituent and one N-alkyl substituent,and the like. The total number of carbon atoms in these aliphaticmonoamines preferably does not exceed about 40 and usually does notexceed about 20 carbon atoms. Specific examples of such monoaminesinclude ethylamine, di-ethylamine, n-butylamine, di-n-butylamine,allylamine, isobutylamine, cocoamine, stearylamine, laurylamine,methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine,octadecylamine, and the like. Examples of cycloaliphatic-substitutedaliphatic amines, aromatic-substituted aliphatic amines, andheterocyclic-substituted aliphatic amines, include2-(cyclohexyl)-ethylamine, benzylamine, phenylethylamine, and3-(furylpropyl) amine.

Cycloaliphatic monoamines are those monoamines wherein there is onecycloaliphatic substituent attached directly to the amino nitrogenthrough a carbon atom in the cyclic ring structure. Examples ofcycloaliphatic monoamines include cyclohexylamines, cyclopentylamines,cyclohexenylamines, cyclopentenylamines,

N-ethyl-cyclohexylamines, dicyclohexylamines, and the like. Examples ofaliphatic-substituted, aromatic-substituted, andheterocyclic-substituted cycloaliphatic monoamines includepropyl-substituted cyclohexylamines, phenyl-substitutedcyclopentylamines and pyranyl-substituted cyclohexylamine.

Aromatic monoamines include those monoamines wherein a carbon atom ofthe aromatic ring structure is attached directly to the amino nitrogen.The aromatic ring will usually be a mononuclear aromatic ring (i.e., onederived from benzene) but can include fused aromatic rings, especiallythose derived from naphthalene. Examples of aromatic monoamines includeaniline, di(para-methylphenyl) amine, naphthylamine, N-(n-butyl)aniline, and the like. Examples of aliphatic-substituted,cycloaliphatic-substituted, and heterocyclic-substituted aromaticmonoamines include para-ethoxyaniline, paradodecylamine,cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.

Heterocyclic polyamines can also be used. As used herein, theterminology “heterocyclic polyamine” is intended to describe thoseheterocyclic amines containing at least two primary amino groups, atleast two secondary amino groups, or at least one of each, and at leastone nitrogen as a heteroatom in the heterocyclic ring. As long as thereis present in the heterocyclic polyamines at least two primary aminogroups, at least two secondary amino groups, or at least one of each,the hetero-N atom in the ring can be a tertiary amino nitrogen; that is,one that does not have hydrogen attached directly to the ring nitrogen.The hetero-N atom can be one of the secondary amino groups; that is, itcan be a ring nitrogen with hydrogen directly attached to it.Heterocyclic amines can be saturated or unsaturated and can containvarious substituents such as nitro, alkoxy, alkyl mercapto, alkyl,alkenyl, aryl, alkaryl, or aralkyl substituents. Generally, the totalnumber of carbon atoms in the substituents will not exceed about 20.Heterocyclic amines can contain heteroatoms other than nitrogen,especially oxygen and sulfur. Obviously they can contain more than onenitrogen heteroatom. The 5- and 6-membered heterocyclic rings arepreferred.

Among the suitable heterocyclic polyamines are the aziridines,azetidines, azolidines, tetra- and di-hydro pyridines, pyrroles,indoles, piperidines, imidazoles, di- and tetrahydroimidazoles,piperazines, isoindoles, purines, morpholines, thiomorpholines,N-aminoalkylmorpholines, N-aminoalkylthiomorpholines,N-aminoalkylpiperazines, N,N′-di-aminoalkylpiperazines, azepines,azocines, azonines, azecines and tetra-, di- and perhydro-derivatives ofeach of the above and mixtures of two or more of these heterocyclicamines. Useful heterocyclic polyamines are the saturated 5- and6-membered heterocyclic polyamines containing only nitrogen, oxygenand/or sulfur in the hetero ring, especially the piperidines,piperazines, thiomorpholines, morpholines, pyrrolidines, and the like.Usually the aminoalkyl substituents are substituted on a nitrogen atomforming part of the hetero ring. Specific examples of such heterocyclicamines include N-aminoethylpiperazine and N,N′-diaminoethylpiperazine.

Hydrazine and substituted-hydrazines can also be used. The substituentswhich may be present on the hydrazine include alkyl, alkenyl, aryl,aralkyl, alkaryl, and the like. Usually, the substituents are alkyl,especially lower alkyl, phenyl, and substituted phenyl such as loweralkoxy-substituted phenyl or lower alkyl-substituted phenyl. Specificexamples of substituted hydrazines are methylhydrazine,N,N-dimethylhydrazine, N,N′-dimethylhydrazine, phenyl-hydrazine,N-phenyl-N′-ethylhydrazine, N-(para-tolyl)-N′-(n-butyl)-hydrazine,N-(para-nitrophenyl)-hydrazine, N-(para-nitrophenyl)-N-methylhydrazine,N,N′-di-(para-chlorophenol)-hydrazine, N-phenyl-N′-cyclohexylhydrazine,and the like.

Another group of amines suitable for use in this invention are branchedpolyalkylene polyamines. The branched polyalkylene polyamines arepolyalkylene polyamines wherein the branched group is a side chaincontaining on the average at least one nitrogen-bonded aminoalkylenegroup per nine amino units present on the main chain; for example, 1-4of such branched chains per nine units on the main chain, but preferablyone side chain unit per nine main chain units. Thus, these polyaminescontain at least three primary amino groups and at least one tertiaryamino group. These amines may be expressed by the formula:NH₂—(R—NH)_(x)N(R)((R—NH)_(z)—R—NH₂)]_(y) wherein R is an alkylenegroup such as ethylene, propylene, butylene and other homologs (bothstraight chained and branched), etc., but preferably ethylene; and x, yand z are integers; x is in the range of from about 4 to about 24 ormore, preferably from about 6 to about 18; y is in the range of from 1to about 6 or more, preferably from 1 to about 3; and z is in the rangeof from zero to about 6, preferably from zero to about 1. The x and yunits may be sequential, alternative, orderly or randomly distributed. Auseful class of such polyamines includes those of the formula:NH₂(R—N(H))₅—N(R)(R—NH₂)—(R—N(H))₂_(n)—H wherein n is an integer inthe range of from 1 to about 20 or more, preferably in the range of from1 to about 3, and R is preferably ethylene, but may be propylene,butylene, etc. (straight chained or branched). U.S. Pat. Nos. 3,200,106and 3,259,578 are incorporated herein by reference for their disclosuresrelative to said polyamines.

Suitable polyamines also include polyoxyalkylene polyamines, e.g.,polyoxyalkylene diamines and polyoxyalkylene triamines, having averagemolecular weights ranging from about 200 to about 4000, preferably fromabout 400 to 2000. Examples of these polyoxyalkylene polyamines includethose amines represented by the formula:NH₂-Alkylene-(O-Alkylene)_(m)-NH₂ wherein m has a value of from about 3to about 70, preferably from about 10 to about 35.R-[-Alkylene-(O-Alkylene)_(n)-NH₂]₃₋₆ wherein n is a number in the rangeof from 1 to about 40, with the proviso that the sum of all of the n'sis from about 3 to about 70 and generally from about 6 to about 35, andR is a polyvalent saturated hydrocarbyl group of up to about 10 carbonatoms having a valence of from about 3 to about 6. The alkylene groupsmay be straight or branched chains and contain from 1 to about 7 carbonatoms, and usually from 1 to about 4 carbon atoms. The various alkylenegroups present within the above formulae may be the same or different.

Useful polyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from about 200 to about 2000. Thepolyoxyalkylene polyamines are commercially available from the Texacounder the trade name “Jeffamine.” U.S. Pat. Nos. 3,804,763 and 3,948,800are incorporated herein by reference for their disclosure of suchpolyoxyalkylene polyamines.

Useful polyamines are the alkylene polyamines, including thepolyalkylene polyamines, as described in more detail hereafter. Thealkylene polyamines include those conforming to the formula:(R)(R)N-(Alkylene-N(R))_(n)—R′ wherein n is from 1 to about 10,preferably from 1 to about 7; each R and R′ is independently a hydrogenatom, a hydrocarbyl group or a hydroxy-substituted hydrocarbyl grouphaving up to about 700 carbon atoms, preferably up to about 100 carbonatoms, more preferably up to about 50 carbon atoms, more preferably upto about 30 carbon atoms, with the proviso that at least one of R and atleast one of R′ are hydrogen; and the “Alkylene” group has from about 1to about 18 carbon atoms, preferably from 1 to about 4 carbon atoms,with the preferred Alkylene being ethylene or propylene. Useful alkylenepolyamines are those wherein each R and each R′ is hydrogen with theethylene polyamines, and mixtures of ethylene polyamines beingparticularly preferred. Such alkylene polyamines include methylenepolyamines, ethylene polyamines, butylene polyamines, propylenepolyamines, pentylene polyamines, hexylene polyamines, heptylenepolyamines, etc. The higher homologs of such amines and relatedaminoalkyl-substituted piperazines are also included.

Alkylene polyamines that are useful include ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, pentaethylenehexamine, propylene diamine, trimethylene diamine, hexamethylenediamine, decamethylene diamine, octamethylene diamine,di(heptamethylene) triamine, tripropylene tetramine, tetraethylenepentamine, trimethylene diamine, pentaethylene hexamine,di(trimethylene) triamine, N-(2-aminoethyl) piperazine, 1,4-bis(2-aminoethyl) piperazine, and the like. Higher homologs as are obtainedby condensing two or more of the above-illustrated alkylene amines areuseful as amines in this invention as are mixtures of two or more of anyof the aforedescribed polyamines.

Ethylene polyamines, such as those mentioned above, are described indetail under the heading “Diamines and Higher Amines, Aliphatic” in TheEncyclopedia of Chemical Technology, Third Edition, Kirk-Othmer, Volume7, pp. 580-602, a Wiley-Interscience Publication, John Wiley and Sons,1979, these pages being incorporated herein by reference. Such compoundsare prepared most conveniently by the reaction of an alkylene chloridewith ammonia or by reaction of an ethylene imine with a ring-openingreagent such as ammonia, etc. These reactions result in the productionof the somewhat complex mixtures of alkylene polyamines, includingcyclic condensation products such as piperazines.

Alkoxylated alkylene polyamines (e.g., N,N-1(diethanol)-ethylenediamine) can be used. Such polyamines can be made by reacting alkyleneamines (e.g., ethylenediamine) with one or more alkylene oxides (e.g.,ethylene oxide, octadecene oxide) of two to about 20 carbons. Similaralkylene oxide-alkanol amine reaction products can also be used such asthe products made by reacting the aforedescribed primary, secondary ortertiary alkanol amines with ethylene, propylene or higher epoxides in a1:1 or 1:2 molar ratio. Reactant ratios and temperatures for carryingout such reactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine,N,N-bis(2-hydroxyethyl)-ethylene-diamine, 1-(2-hydroxyethyl) piperazine,mono(hydroxypropyl)-substituted diethylene triamine,di(hydroxypropyl)-substituted tetraethylene pentamine,N-(3-hydroxybutyl)-tetra-methylene diamine, etc. Higher homologsobtained by condensation of the above-illustrated hydroxy alkylenepolyamines through amino groups or through hydroxy groups are likewiseuseful. Condensation through amino groups results in a higher amineaccompanied by removal of ammonia while condensation through the hydroxygroups results in products containing ether linkages accompanied byremoval of water. Mixtures of two or more of any of the aforesaidpolyamines are also useful.

Useful hydroxyamines can be primary or secondary amines. They can alsobe tertiary amines provided said tertiary amines also contain at leasttwo hydroxyl groups. These hydroxyamines contain at least two >NHgroups, at least two —NH₂ groups, at least one —OH group and at leastone >NH or —NH₂ group, or at least two —OH groups. The terms“hydroxyamine” and “aminoalcohol” describe the same class of compoundsand, therefore, can be used interchangeably.

The hydroxyamines can be primary or secondary alkanol amines or mixturesthereof. Such amines can be represented, respectfully, by the formulae:(H)(R)N—R′—OH wherein R is a hydrocarbyl group of one to about eightcarbon atoms or hydroxylsubstituted hydrocarbyl group of two to abouteight carbon atoms and R′ is a divalent hydrocarbyl group of about twoto about 18 carbon atoms. The group —R′—OH in such formulae representsthe hydroxyl-substituted hydrocarbyl group. R′ can be an acyclic,alicyclic or aromatic group. Typically, R′ is an acyclic straight orbranched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Typically, R is a loweralkyl group of up to seven carbon atoms. The primary or secondaryalkanol amines may contain slightly larger R and R′ groups, and maycontain up to about 40 carbon atoms.

The hydroxyamines can also be ether N-(hydroxy-substitutedhydrocarbyl)amines. These are hydroxyl-substituted poly(hydrocarbyloxy)analogs of the above-described primary and secondary alkanol amines(these analogs also include hydroxyl-substituted oxyalkylene analogs).Such N-(hydroxyl-substituted hydrocarbyl) amines can be convenientlyprepared by reaction of epoxides with aforedescribed amines and can berepresented by the formulae: H₂N—R′—OH and (H)(R)N—R′—OH wherein x is anumber from about 2 to about 15 and R and R′ are as described above.

Polyamine analogs of these hydroxy amines, particularly alkoxylatedalkylene polyamines (e.g., N,N-(diethanol)-ethylene diamine) can also beused. Such polyamines can be made by reacting alkylene amines (e.g.,ethylenediamine) with one or more alkylene oxides (e.g., ethylene oxide,octadecene oxide) of two to about 20 carbons. Similar alkyleneoxide-alkanol amine reaction products can also be used such as theproducts made by reacting the aforedescribed primary or secondaryalkanol amines with ethylene, propylene or higher epoxides in a 1:1 or1:2 molar ratio. Reactant ratios and temperatures for carrying out suchreactions are known to those skilled in the art.

Specific examples of alkoxylated alkylene polyamines includeN-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl) ethylenediamine, 1-(2-hydroxyethyl) piperazine, mono(hydroxypropyl)-substituteddiethylene triamine, di(hydroxypropyl)-substituted tetraethylenepentamine, N-(3-hydroxybutyl)-tetramethylene diamine, etc. Higherhomologs obtained by condensation of the above-illustratedhydroxyalkylene polyamines through amino groups or through hydroxygroups are likewise useful. Condensation through amino groups results ina higher amine accompanied by removal of ammonia, while condensationthrough the hydroxy groups results in products containing ether linkagesaccompanied by removal of water. Mixtures of two or more of any of theaforesaid mono- or polyamines are also useful.

Examples of the N-(hydroxyl-substituted hydrocarbyl) amines includemono-, di-, and triethanol amine, diethylethanol amine, di-(3-hydroxylpropyl) amine, N-(3-hydroxyl butyl) amine, N-(4-hydroxyl butyl) amine,N,N-di-(2-hydroxyl propyl) amine, N-(2-hydroxyl ethyl) morpholine andits thio analog, N-(2-hydroxyl ethyl) cyclohexyl amine, N-3-hydroxylcyclopentyl amine, o-, m- and p-aminophenol, N-(hydroxyl ethyl)piperazine, N,N′-di(hydroxyl ethyl) piperazine, and the like.

Further, hydroxyamines are the hydroxy-substituted primary aminesdescribed in U.S. Pat. No. 3,576,743 by the general formula R^(a)—NH₂wherein R^(a) is a monovalent organic group containing at least onealcoholic hydroxy group. The total number of carbon atoms in R^(a)preferably does not exceed about 20. Hydroxy-substituted aliphaticprimary amines containing a total of up to about 10 carbon atoms areuseful. The polyhydroxy-substituted alkanol primary amines wherein thereis only one amino group present (i.e., a primary amino group) having onealkyl substituent containing up to about 10 carbon atoms and up to about6 hydroxyl groups are useful. These alkanol primary amines correspond toR^(a)—NH₂ wherein R^(a) is a mono- or polyhydroxy-substituted alkylgroup. Specific examples of the hydroxy-substituted primary aminesinclude 2-amino-1-butanol, 2-amino-2-methyl-1-propanol,p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxypropyl)-N′-(beta-amino ethyl)-piperazine,tris-(hydroxymethyl) amino methane (also known as trismethylolaminomethane), 2-amino-1-butanol, ethanolamine,beta-(beta-hydroxyethoxy)-ethyl amine, glucamine, glusoamine,4-amino-3-hydroxy-3-methyl-1-butene (which can be prepared according toprocedures known in the art by reacting isoprene-oxide with ammonia),N-3-(aminopropyl)-4-(2-hydroxyethyl)piperidine,2-amino-6-methyl-6-heptanol, 5-amino-1-pentanol,N-(beta-hydroxyethyl)1,3diamino propane, 1,3-diamino-2-hydroxypropane,N-(beta-hydroxyethoxyethyl)ethylene diamine, trismethylolaminomethaneand the like. U.S. Pat. No. 3,576,743 is incorporated herein byreference.

Hydroxyalkyl alkylene polyamines having one or more hydroxyalkylsubstituents on the nitrogen atoms, are also useful. Usefulhydroxyalkyl-substituted alkylene polyamines include those in which thehydroxyalkyl group is a lower hydroxyalkyl group, i.e., having less thaneight carbon atoms. Examples of such hydroxyalkyl-substituted polyaminesinclude N-(2-hydroxyethyl) ethylene diamine, N,N-bis(2-hydroxyethyl)ethylene diamine, 1-(2-hydroxyethyl)-piperazine,monohydroxypropyl-substituted diethylene triamine,dihydroxypropylsubstituted tetraethylene pentamine, N-(3-hydroxybutyl)tetramethylene diamine, etc. Higher homologs as are obtained bycondensation of the above-illustrated hydroxy alkylene polyaminesthrough amino groups or through hydroxy groups are likewise useful.Condensation through amino groups results in a higher amine accompaniedby removal of ammonia and condensation through the hydroxygroups resultsin products containing ether linkages accompanied by removal of water.

Useful tertiary amines include be aliphatic, cycloaliphatic, aromatic orheterocyclic, including aliphatic-substituted aromatic,aliphatic-substituted cycloaliphatic, aliphatic-substitutedheterocyclic, cycloaliphatic-substituted aliphatic, cycloaliphaticsubstituted aromatic, cycloaliphatic-substituted heterocyclic,aromatic-substituted aliphatic, aromatic-substituted cycloaliphatic,aromatic-substituted heterocyclic, heterocyclic-substituted aliphatic,heterocyclic-substituted cycloaliphatic and heterocyclic-substitutedaromatic amines. These tertiary amines may be saturated or unsaturated.If unsaturated, the amine is preferably free from acetylenicunsaturation. The tertiary amines may also contain non-hydrocarbonsubstituents or groups as long as these groups do not significantlyinterfere with the reaction. Such non-hydrocarbon substituents or groupsinclude lower alkoxy, lower alkyl, mercapto, nitro, and interruptinggroups such as —O— and—S— (e.g., as in such groups as —CH₂CH₂—X—CH₂CH₂—where X is —O— or —S—).

The monoamines can be represented by the formula N(R¹)(R²)(R³) whereinR¹, R², and R³ are the same or different hydrocarbyl groups. Preferably,R¹, R², and R³ are independently hydrocarbyl groups of from 1 to about20 carbon atoms.

Examples of useful tertiary amines include trimethyl amine, triethylamine, tripropyl amine, tributyl amine, monomethyldiethylamine,monoethyldimethyl amine, dimethylpropyl amine, dimethylbutyl amine,dimethylpentyl amine, dimethylhexyl amine, dimethylheptyl amine,dimethyloctyl amine, dimethylnonyl amine, dimethyldecyl amine,dimethylphenyl amine, N,N-dioctyl-1-octanamine,N,N-di-dodecyl-1-dodecanamine tricoco amine, trihydrogenated tallowamine, N-methyldihydrogenated tallow amine, N,N-dimethyl-1-dodecanamine,N,N-dimethyl-1-tetradecanamine, N,N-dimethyl-1-hexadecanamine,N,N-dimethyl-1-octadecanamine, N,N-dimethylcocoamine,N,N-dimethylsoyaamine, N,N-dimethylhydrogenated tallow amine, etc.

Useful tertiary alkanol amines are represented by the formula(R)(R)N—R′—OH wherein each R is independently a hydrocarbyl group of oneto about eight carbon atoms or hydroxyl-substituted hydrocarbyl group oftwo to about eight carbon atoms and R′ is a divalent hydrocarbyl groupof about two to about 18 carbon atoms. The group —R′—OH in such formularepresents the hydroxyl-substituted hydrocarbyl group. R′ can be anacyclic, alicyclic or aromatic group. Typically, R′ is an acyclicstraight or branched alkylene group such as an ethylene, 1,2-propylene,1,2-butylene, 1,2-octadecylene, etc. group. Where two R groups arepresent in the same molecule they can be joined by a directcarbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen orsulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Examples ofsuch heterocyclic amines include N-(hydroxyl lower alkyl)-morpholines,thiomorpholines, -piperidines, -oxazolidines, -thiazolidines and thelike. Typically, however, each R is a lower alkyl group of up to sevencarbon atoms. The hydroxyamines can also be an etherN-(hydroxy-substituted hydrocarbyl)amine. These are hydroxyl-substitutedpoly-(hydrocarbyloxy) analogs of the above described hydroxy amines(these analogs also include hydroxyl-substituted oxyalkylene analogs).Such N-(hydroxyl-substituted hydrocarbyl) amines can be convenientlyprepared by reaction of epoxides with the amines described above and canbe represented by the formula: (R)(R)N—(R′—O)_(x)H wherein x is a numberfrom about 2 to about 15 and R and R′ are as described above.

Useful polyamines include the alkylene polyamines discussed above aswell as alkylene polyamines with only one or no hydrogens attached tothe nitrogen atoms. Thus, the alkylene polyamines useful as neutralizingcomponents include those conforming to the formula: (R)(R)N—(R′—O)_(x)—Hwherein x is from 1 to about 10, from 1 to about 7; each R isindependently a hydrogen atom, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group having up to about 700 carbonatoms, preferably up to about 100 carbon atoms, more preferably up toabout 50 carbon atoms, more preferably up to about 30 carbon atoms; andthe “Alkylene” group has from about 1 to about 18 carbon atoms,preferably from 1 to about 4 carbon atoms, with the preferred Alkylenebeing ethylene or propylene.

The alkali and alkaline earth metals that are useful as neutralizingcomponents can be any alkali or alkaline earth metal. The alkali metalsare preferred. Sodium and potassium are particularly preferred. Thealkali and alkaline earth metal compounds that are useful include, forexample, the oxides, hydroxides and carbonates. Sodium hydroxide andpotassium hydroxide are particularly preferred.

The invention further provides a process of making the describedemulsifier component. The process comprises the steps of: Step (I)reacting a first hydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an (optionally linear)alkylene glycol; wherein the first hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing at least 20carbon atoms; and wherein the second hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing less than 20carbon atoms; resulting in an additive comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; Step (II)providing said additive for use as an emulsifier component precursor;Step (III) converting said additive to an emulsifier component byreacting said additive with a neutralizing component. Any of theemulsifier components described above may be prepared by this process.

In some embodiments, the process may be described as initially reactingthe first hydrocarbyl-substituted acylating agent and the secondhydrocarbyl-substituted acylating agent the alkylene glycol to form anadditive, and thereafter providing the additive, as described above, toan end use who may then use the additive to form the emulsifiercomponent of his/her choosing by reacting said intermediate with theneutralizing component to form the desired salt.

The ratio of reactants utilized in the preparation of either theadditive (and/or the emulsifier component precursor) emulsifiercomponent may be varied over a wide range. Generally, for eachequivalent of each of the acylating agents, at least about oneequivalent of alkylene glycol is used. From about 0.1 to about 2equivalents or more of neutralizing component are used for eachequivalent of components acylating agents, respectively. The upper limitof alkylene glycol is about 2 equivalents of alkylene glycol for eachequivalent of acylating agents. Generally the ratio of equivalents ofacylating agents is about 0.5 to about 2, with about 1:1 beingpreferred. Preferred amounts of the reactants are about 2 equivalents ofthe alkylene glycol and from about 0.1 to about 2 equivalents of each ofneutralizing component for each equivalent of each acylating agent.

The number of equivalents of the acylating agents depends on the totalnumber of carboxylic functions present in each. In determining thenumber of equivalents for each of the acylating agents, those carboxylfunctions which are not capable of reacting as a carboxylic acidacylating agent are excluded. In general, however, there is oneequivalent of acylating agent for each carboxy group in these acylatingagents. For example, there would be two equivalents in an anhydridederived from the reaction of one mole of olefin polymer and one mole ofmaleic anhydride. Conventional techniques are readily available fordetermining the number of carboxyl functions (e.g., acid number,saponification number) and, thus, the number of equivalents of each ofthe acylating agents can be readily determined by one skilled in theart.

An equivalent weight of a polyamine is the molecular weight of thepolyamine divided by the total number of nitrogens present in themolecule where tertiary amino groups are counted. Thus, ethylene diaminehas an equivalent weight equal to one-half of its molecular weight;diethylene triamine has an equivalent weight equal to one-third itsmolecular weight. The equivalent weight of a commercially availablemixture of polyalkylene polyamine can be determined by dividing theatomic weight of nitrogen (14) by the % N contained in the polyamine;thus, a polyamine mixture having a % N of 34 would have an equivalentweight of 41.2. An equivalent weight of ammonia or a monoamine is itsmolecular weight.

An equivalent weight of polyhydric alcohol is its molecular weightdivided by the total number of hydroxyl groups present in the molecule.Thus, an equivalent weight of ethylene glycol is one-half its molecularweight.

An equivalent weight of a hydroxyamine would be its molecular weightdivided by the total number of nitrogen groups present in the molecule.Thus, dimethylethanolamine would have an equivalent weight equal to itsmolecular weight; ethanolamine would also have an equivalent weightequal to its molecular weight.

An equivalent weight of an alkali or alkaline earth metal is itsmolecular weight. An equivalent weight of an alkali or alkaline earthmetal compound is its molecular weight divided by the number of alkalior alkaline earth metal atoms present in the molecule.

The acylating agents can be reacted with the alkylene glycol accordingto conventional ester and/or amide forming techniques. This normallyinvolves heating acylating agents with the alkylene glycol optionally inthe presence of a normally liquid, substantially inert, organic liquidsolvent/diluent.

The reactions between the additive and the neutralizing component arecarried out under salt forming conditions using conventional techniques.Typically, the components are mixed together and heated to a temperaturein the range of about 20° C. up to the decomposition temperature of thereaction component and/or product having the lowest such temperature,optionally, in the presence of a normally liquid, substantially inertorganic liquid solvent/diluent, until the desired product has formed.

The invention further provides a method and/or use of the additivedescribed above as part of a process of customizing an emulsifiercomponent in a composition. This method and/or use includes the stepsof: Step (I) preparing an additive by reacting a firsthydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an (optionally linear)alkylene glycol; wherein the first hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing at least 20carbon atoms; and wherein the second hydrocarbyl-substituted acylatingagent comprises a hydrocarbyl substituent group containing less than 20carbon atoms; resulting in an additive comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; Step (II)supplying said additive into a composition that requires an emulsifiercomponent; Step (III) converting said additive, in said composition, toan emulsifier component by reacting said additive with a neutralizingcomponent; resulting in a customized emulsifier component.

Functional Fluid Composition

The emulsion components described herein may be used to make functionalcompositions such as oil-in-water emulsions which comprise a continuouswater phase, a discontinuous organic phase, the emulsifying composition,and additives related to the function to be performed by the functionalfluid. The discontinuous organic phase is preferably present at a levelof at least about 1% by weight, more preferably in the range of fromabout 1% to about 50% by weight, more preferably in the range of fromabout 1% to about 20% by weight based on the total weight of emulsion.The continuous water phase is preferably present at a level of about 99%by weight, more preferably at a level in the range of from about 50% toabout 99% by weight, more preferably from about 80% to about 99% byweight based on the total weight of said emulsion. The salt compositionsof the invention are preferably present at a level in the range of fromabout 1% to about 100% by weight, more preferably from about 20% toabout 80% by weight based on the total weight of the organic phase. Whenthe emulsifier is 100% of the organic phase, the emulsifier is acting toform an emulsion of itself in the water phase, and the organic phase isthe emulsifier.

The oil can include most liquid hydrocarbons, for example, paraffinic,olefinic, naphthenic, aromatic, saturated or unsaturated hydrocarbons.In general, the oil is a water-immiscible, emulsifiable hydrocarbon thatis either liquid at room temperature. Oils from a variety of sources,including natural and synthetic oils and mixtures thereof may be used.

Natural oils include animal oils and vegetable oils (e.g., castor oil,lard oil) as well as solvent-refined or acid-refined mineral oils of theparaffinic, naphthenic, or mixed paraffin-naphthenic types. Oils derivedfrom coal or shale are also useful. Synthetic oils include hydrocarbonoils and halo-substituted hydrocarbon oils such as polymerized andinterpolymerized olefins e.g., polybutylenes, polypropylenes,propylene-isobutylene copolymers, chlorinated polybutylenes; alkylbenzenes, e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl) benzenes, and the like.

Another suitable class of synthetic oils that can be used comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid,fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl malonic acids, etc.) with a variety of alcohols(e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexylalcohol, ethylene glycol, diethylene glycol monoether, propylene glycol,pentaerythritol, etc.). Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)-sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid, and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another class ofuseful oils. These include tetraethyl-silicate, tetraisopropylsilicate,tetra-(2-ethylhexyl)-silicate, tetra-(4-methylhexyl)-silicate, tetra(p-tert-butylphenyl)-silicate, hexyl-(4-methyl-2-pentoxy)-di-siloxane,poly(methyl)-siloxanes, poly-(methylphenyl)-siloxanes, etc. Other usefulsynthetic oils include liquid esters of phosphorus-containing acid(e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid, etc.), polymeric tetrahydrofurans, and the like.

Unrefined, refined and rerefined oils (and mixtures of each with eachother) of the type disclosed hereinabove can be used. Unrefined oils arethose obtained directly from a natural or synthetic source withoutfurther purification treatment. For example, a shale oil obtaineddirectly from a retorting operation, a petroleum oil obtained directlyfrom distillation or ester oil obtained directly from an esterificationprocess and used without further treatment would be an unrefined oil.Refined oils are similar to the unrefined oils except that they havebeen further treated in one or more purification steps to improve one ormore properties. Many such purification techniques are known to those ofskill in the art such as solvent extraction, distillation, acid or baseextraction, filtration, percolation, etc. Rerefined oils are obtained byprocesses similar to those used to obtain refined oils applied torefined oils which have been already used in service. Such rerefinedoils are also known as reclaimed or reprocessed oils and often areadditionally processed by techniques directed toward removal of spentadditives and oil breakdown products.

Examples of useful oils include a white mineral oil available from WitcoChemical Company under the trade designation KAYDOL; a white mineral oilavailable from Shell under the trade designation ONDINA; and a mineraloil available from Pennzoil under the trade designation N-750-HT.

Optional additional materials may be incorporated in the composition ofthe present invention. Typical finished compositions may includelubricity agents, anti-wear agents, dispersants, corrosion inhibitors,other surfactants, and the like. The emulsions of the present inventionare shelf stable, which means they exhibit shelf stability of at leastsix months and typically one year or more.

A preferred method for making the emulsions of the invention comprisesthe steps of (1) mixing the emulsifier with the oil phase, (2) mixingthe additives with the oil phase, (3) stirring the oil phase with thewater phase to form a oil-in-water emulsion. Mixing of the oil with theappropriate additives may be conducted in any suitable mixing apparatus.Any type of apparatus capable of either low or high shear mixing may beused to mix the oil and water phases to prepare these oil-in-wateremulsions.

The amount of each chemical component described is presented exclusiveof any solvent or diluent oil, which may be customarily present in thecommercial material, that is, on an active chemical basis, unlessotherwise indicated. However, unless otherwise indicated, each chemicalor composition referred to herein should be interpreted as being acommercial grade material which may contain the isomers, by-products,derivatives, and other such materials which are normally understood tobe present in the commercial grade.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude:

-   -   hydrocarbon substituents, that is, aliphatic (e.g., alkyl or        alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl)        substituents, and aromatic-, aliphatic-, and        alicyclic-substituted aromatic substituents, as well as cyclic        substituents wherein the ring is completed through another        portion of the molecule (e.g., two substituents together form a        ring);    -   substituted hydrocarbon substituents, that is, substituents        containing non-hydrocarbon groups which, in the context of this        invention, do not alter the predominantly hydrocarbon nature of        the substituent (e.g., halo (especially chloro and fluoro),        hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and        sulfoxy);    -   hetero substituents, that is, substituents which, while having a        predominantly hydrocarbon character, in the context of this        invention, contain other than carbon in a ring or chain        otherwise composed of carbon atoms and encompass substituents as        pyridyl, furyl, thienyl and imidazolyl. Heteroatoms include        sulfur, oxygen, and nitrogen. In general, no more than two, or        no more than one, non-hydrocarbon substituent will be present        for every ten carbon atoms in the hydrocarbyl group;        alternatively, there may be no non-hydrocarbon substituents in        the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

The invention may be better understood with reference to the followingnon-limiting examples.

EXAMPLES

Several examples are prepared to demonstrate the invention.

Comparative Example 1

A preformed salt emulsifier component is prepared in a reaction vesselby adding 33.33 pbw of 1000 Mn highly reacted polyisobutylene succinicanhydride, 28.41 pbw of hexadecenyl succinic anhydride, and 23.15 pbwISO 22 mineral oil. The mixture is heated to 99° C. under a nitrogenpurge. Then 3.87 pbw of ethylene glycol is slowly added to the reactionvessel and the resulting mixture is held at about 99° C. for 4 hours.The reaction mixture is cooled to 68° C. before adding 11.24 pbwdimethylethanolamine. The following reaction is held below 93° C. Theamine salted product is then cooled to ambient temperature.

Inventive Example 2

An unsalted ester acid emulsifier component is prepared in the lab. In areaction vessel, 40.45 parts by weight (pbw) of 1000 number averagemolecular weight (Mn) highly reacted polyisobutylene succinic anhydride,34.83 pbw of hexadecenyl succinic anhydride, and 20.00 pbw ISO 22mineral oil are mixed and heated to 135° C. under a nitrogen purge. Then4.72 pbw of ethylene glycol is slowly added to the reaction vessel andthe resulting mixture is held at about 135° C. for 4 hours. Theresulting unsalted product is then cooled to ambient temperature andcollected.

Using the additives of Comparative Example 1 and Inventive Example 2, aset of additive packages (Examples A-1 to G-1) are prepared and thenused to prepare emulsion samples (Examples A-2 to G-2) to evaluate theemulsion performance of the additives. The formulations of the additivepackages tested are summarized in the table below, where all values areweight percent unless otherwise noted. The additional additives used ineach example are identical and include a low HLB emulsifier, a fattyacid salt, a corrosion inhibitor, and a biocide.

TABLE 1 Additive Packages: Inv Inv Inv Comp Inv Inv Inv Ex A-1 Ex B-1 ExC-1 Ex D-1 Ex E-1 Ex F-1 Ex G-1 Comparative Ex 1 0 0 0 8.0 0 0 0 (DMEA)Inventive Ex 2 7.30 6.47 7.00 0 4.56 4.04 4.37 Amine MEA TEA DMEA 0 MEATEA DMEA (Type & wt %) 0.70 1.53 1.00 0.44 0.96 0.63 AdditionalAdditives 15.5 15.5 15.5 16.0 16.05 16.05 16.05 ISO 22 Paraffinic oilBalance Balance Balance Balance Balance Balance Balance

All of the additive packages described in table above are prepared byblending the ingredients in the order listed and heating the mixtures to50° C. with moderate stirring for about one hour.

Each additive package is then used to prepare an emulsion. Each emulsionsample is prepared by adding water so that the concentration of theadditive package is the same in each emulsion sample (5% by weight).Each emulsion sample is shaken vigorously shaken in a graduated cylinderand then allowed to stand for 24 hours before being rating forstability, by measuring the amount, or percent, of oil visible in thesample, and the amount, or percent, of cream visible in the sample. Theless oil and cream visible, the more stable the emulsion, and so themore effective the additive package, and so the emulsifier additive. Aformulation is considered acceptable for use if it has 0% or a trace ofoil and no more than 0.5% cream after 24 hours.

An industry foam test was also conducted on some of the emulsionsamples. In this test, 200 ml of the emulsion example is placed in aSunbeam cake mixer and sheared at high speed for 300 seconds. Then thetime, in seconds, for the foam to collapse after the mixer is turned offis recorded, and this time is reported as the foam break and/or collapsetime. The shorter the time it takes for the foam to collapse, the betterthe result, but a result of 60 seconds or less is generally consideredacceptable.

The results of the testing are summarized in the table below.

TABLE 2 Results Inv Inv Inv Comp Inv Inv Inv Ex A-2 Ex B-2 Ex C-2 Ex D-2Ex E-2 Ex F-2 Ex G-2 Emulsifier Inv Ex 2 Inv Ex 2 Inv Ex 2 Comp Inv Ex 2Inv Ex 2 Inv Ex 2 Used in and and and Ex 1 and and and Additive MEA TEADMEA (DMEA) MEA TEA DMEA Package Concentration 0.4 wt % 0.4 wt % 0.4 wt% 0.4 wt % 0.25 wt % 0.25 wt % 0.25 wt % of Emulsifier in EmulsionStability 0/0 O/Trace O/Trace O/Trace O/Trace O/Trace O/Trace % oil/%cream PASS PASS PASS PASS PASS PASS PASS 114 ppm water Stability O/TraceO/Trace O/Trace 0/0.5 O/Trace O/Trace O/Trace % oil/% cream PASS PASSPASS FAIL PASS PASS PASS 600 ppm water Foam Break 132 sec 7 sec 9 sec <5sec 9 sec <5 sec <5 sec 114 ppm water

The results above show the additives of the present invention provideacceptable stability and emulsifier performance while also providing theadding flexibility of allowing in-situ salt formation.

Each of the documents referred to above is incorporated herein byreference, including any prior applications, whether or not specificallylisted above, from which priority is claimed. The mention of anydocument is not an admission that such document qualifies as prior artor constitutes the general knowledge of the skilled person in anyjurisdiction. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” It is to be understood that the upper and lower amount, range,and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.

As used herein, the transitional term “comprising,” which is synonymouswith “including,” “containing,” or “characterized by,” is inclusive oropen-ended and does not exclude additional, un-recited elements ormethod steps. However, in each recitation of “comprising” herein, it isintended that the term also encompass, as alternative embodiments, thephrases “consisting essentially of” and “consisting of,” where“consisting of” excludes any element or step not specified and“consisting essentially of” permits the inclusion of additionalun-recited elements or steps that do not materially affect the basic andnovel characteristics of the composition or method under consideration.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention. In this regard, the scope of the invention is to be limitedonly by the following claims.

What is claimed is:
 1. An additive comprising (i) a functional groupderived from a first hydrocarbyl-substituted acylating agent and (ii) afunctional group derived from a second hydrocarbyl-substituted acylatingagent, where the functional groups (i) and (ii) are coupled by afunctional group derived from an alkylene glycol; wherein the firsthydrocarbyl-substituted acylating agent comprises a hydrocarbylsubstituent group containing at least about 20 carbon atoms; and whereinthe second hydrocarbyl-substituted acylating agent comprises ahydrocarbyl substituent group containing less than about 20 carbonatoms.
 2. The additive of claim 1 wherein the firsthydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight greater than about
 400. 3. The additive of claim 1 or claim 2wherein the first hydrocarbyl-substituted acylating agent comprisespolyisobutylene succinic anhydride, the polyisobutylene group having anumber average molecular weight greater than about
 400. 4. The additiveof any one of claims 1 through 3 wherein the secondhydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight less than about
 280. 5. The additive of any one of claims 1through 4 wherein the second hydrocarbyl-substituted acylating agentcomprises hexadecenyl succinic anhydride.
 6. The additive of any one ofclaims 1 through 5 wherein the alkylene glycol comprises a glycol havingthe general formula HO(CH(R))_(x)—O_(m)—H where each R isindependently H or an alkyl group of 1 to 6 carbon atoms, each x isindependently an integer from 2 to about 10, and m is an integer from 1to about
 10. 7. The additive of any one of claims 1 through 6 whereinthe alkylene glycol is a linear alkylene glycol.
 8. The additive of anyone of claims 1 through 7 wherein the alkylene glycol comprises apoly(ethylene glycol), a poly(1,3-propylene glycol) or a copolymer ofethylene glycol and 1,3-propylene glycol.
 9. The additive of any one ofclaims 1 through 8 wherein the alkylene glycol comprises a glycol havingthe general formula HO—(CH₂)_(x)—OH wherein x is an integer from 2 toabout
 10. 10. The additive of claim 9 wherein the alkylene glycolcomprises ethylene glycol.
 11. The additive of any one of claims 1through 7 wherein the first hydrocarbyl-substituted acylating agentcomprises polyisobutylene succinic anhydride, the polyisobutylene grouphaving a number average molecular weight greater than about 750; whereinthe second hydrocarbyl-substituted acylating agent comprises hexadecenylsuccinic anhydride; and wherein the alkylene glycol comprises ethyleneglycol.
 12. The additive of any of claims 1 through 11 which is reactedwith a neutralizing component comprising an amine.
 13. A process ofmaking an emulsifier component comprising the steps of: I. reacting afirst hydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an alkylene glycol; whereinthe first hydrocarbyl-substituted acylating agent comprises ahydrocarbyl substituent group containing at least about 20 carbon atoms;and wherein the second hydrocarbyl-substituted acylating agent comprisesa hydrocarbyl substituent group containing less than about 20 carbonatoms; resulting in an intermediate comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; II. providing saidintermediate for use as an emulsifier component precursor; andthereafter III. converting said intermediate to an emulsifier componentby reacting said intermediate with a neutralizing component.
 14. Theprocess of claim 13 wherein the first hydrocarbyl-substituted acylatingagent comprises the reaction product of a long chain hydrocarbon with amonounsaturated carboxylic acid; wherein said long chain hydrocarbon hasa number average molecular weight greater than about 400; and whereinthe second hydrocarbyl-substituted acylating agent comprises thereaction product of a long chain hydrocarbon with a monounsaturatedcarboxylic acid; wherein said long chain hydrocarbon has a numberaverage molecular weight less than about 280; wherein the alkyleneglycol comprises a glycol having of the general formulaHO(C(R))_(x)—O_(m)—H wherein each R is independently H or an alkylgroup of 1 to 6 carbon atoms, each x is independently an integer from 2to about 10 and m is an integer from 1 to about
 10. 15. The process ofclaim 13 or claim 14 wherein the alkylene glycol comprises apoly(ethylene glycol), a poly(1,3-propylene glycol) or a copolymer ofethylene glycol and 1,3-propylene glycol.
 16. The process of claim 13 orclaim 14 wherein the alkylene glycol comprises a glycol having thegeneral formula HO—(CH₂)_(x)—OH wherein x is an integer from 2 to about10.
 17. The process of claim 14 wherein the firsthydrocarbyl-substituted acylating agent comprises polyisobutylenesuccinic anhydride having a number average molecular weight greater thanabout 750; wherein the second hydrocarbyl-substituted acylating agentcomprises hexadecenyl succinic anhydride; and wherein the alkyleneglycol comprises ethylene glycol.
 18. The process of any one of claims13 through 17 wherein the neutralizing component comprises an amine. 19.A method of customizing an emulsifier component in a composition, saidmethod comprising the steps of: I. reacting a firsthydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an alkylene glycol; whereinthe first hydrocarbyl-substituted acylating agent comprises ahydrocarbyl substituent group containing at least about 20 carbon atoms;and wherein the second hydrocarbyl-substituted acylating agent comprisesa hydrocarbyl substituent group containing less than about 20 carbonatoms; resulting in an intermediate comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; II. providing saidintermediate for use as an emulsifier component precursor; andthereafter III. converting said intermediate to an emulsifier componentby reacting said intermediate with a neutralizing component; resultingin a customized emulsifier component.
 20. The method of claim 19 whereinthe first hydrocarbyl-substituted acylating agent comprises the reactionproduct of a long chain hydrocarbon with a monounsaturated carboxylicacid; wherein said long chain hydrocarbon has a number average molecularweight greater than about 400; and wherein the secondhydrocarbyl-substituted acylating agent comprises the reaction productof a long chain hydrocarbon with a monounsaturated carboxylic acid;wherein said long chain hydrocarbon has a number average molecularweight less than about 280; wherein the alkylene glycol comprises aglycol having of the general formula HO—(CH₂)_(x)—OH wherein x is aninteger from 2 to about
 10. 21. The method of claim 19 or claim 20wherein the neutralizing component comprises an amine.
 22. An emulsifiercomponent prepared by a process comprising the steps of: I. reacting afirst hydrocarbyl-substituted acylating agent, a secondhydrocarbyl-substituted acylating agent, and an alkylene glycol; whereinthe first hydrocarbyl-substituted acylating agent comprises ahydrocarbyl substituent group containing at least about 20 carbon atoms;and wherein the second hydrocarbyl-substituted acylating agent comprisesa hydrocarbyl substituent group containing less than about 20 carbonatoms; resulting in an intermediate comprising (i) a functional groupderived from said first hydrocarbyl-substituted acylating agent and (ii)a functional group derived from said second hydrocarbyl-substitutedacylating agent, where the functional groups (i) and (ii) are coupled bya functional group derived from said alkylene glycol; II. providing saidintermediate for use as an emulsifier component precursor; andthereafter III. converting said intermediate to an emulsifier componentby reacting said intermediate with a neutralizing component.
 23. Theemulsifier component of claim 22 where said neutralizing componentcomprises an amine.